Use of macrocyclic lactone in augmenting or enhancing aroma or taste of consumable materials

ABSTRACT

Described for use in augmenting or enhancing the aroma or taste of consumable materials including perfume compositions, colognes and perfumed articles, foodstuffs, chewing gums, toothpastes and medicinal products are the cis and/or trans isomers of the macrocyclic lactone defined according to the structure: ##STR1## produced according to the process of first reacting the ester defined according to the structure: ##STR2## with the alkenol having the structure: ##STR3## in order to produce the di-unsaturated ester having the structure: ##STR4## and then causing the said diester to undergo an internal metathesis to form the compound having the structure: ##STR5##

This is a divisional of application Ser. No. 617,584, filed 6/5/84, nowU.S. Pat. No. 4,541,950, which, in turn, is a divisional of applicationfor U.S. Pat. Ser. No. 514,523 filed on 7/18/83, now U.S. Pat. No.4,490,404 issued 12/25/84.

BACKGROUND OF THE INVENTION

This invention relates to the use of the macrocyclic lactone having thestructure: ##STR6## in augmenting or enhancing the aroma or taste ofconsumable materials including perfume compositions, colognes, perfumedarticles, foodstuffs, chewing gums, toothpastes and medicinal products.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the NMR spectrum for the compound produced according toExample I having the structure: ##STR7## (conditions: Field Strength:100 MHz; Solvent: CFCl₃).

FIG. 2 is the infra-red spectrum for the compound having the structure:##STR8## produced according to Example I.

FIG. 3 is the GLC profile for the reaction product of Example IIcontaining the compound having the structure: ##STR9## (conditions: 10%Carbowax column, 10'×0.25" programmed at 150°-225° C. at 8° C. perminute).

FIG. 4 is the NMR spectrum for the trans isomer of the compound havingthe structure: ##STR10## produced according to Example II (conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 5 is the infra-red spectrum for the trans isomer of the compoundhaving the structure: ##STR11## produced according to Example II.

FIG. 6 is the NMR spectrum for the cis isomer of the compound having thestructure: ##STR12## produced according to Example II (conditions: FieldStrength: 100 MHz; Solvent: CFCl₃).

FIG. 7 is the infra-red spectrum for the cis isomer of the compoundhaving the structure: ##STR13## produced according to Example II.

FIG. 8 is a partial side elevation and partial sectional view of anapparatus for forming scented polymer using the compounds definedaccording to the structure: ##STR14## constructed in accordance with theinvention.

FIG. 9 is a section taken along line 9--9 of FIG. 8.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 3 is the GLC profile for the reaction product of Example II(conditions: 10'×0.25" 10% Carbowax column programmed at 150°-225° C. at8° C. per minute). The peak indicated by reference numeral "31" is thepeak for the starting material having the structure: ##STR15##

The peak indicated by reference numeral "32" is the peak for the transisomer of the compound having the structure: ##STR16##

The peak indicated by reference numeral "33" is the peak for the cisisomer of the compound having the structure: ##STR17##

Referring to the drawings in FIGS. 8 and 9 in particular, the inventionembodied therein comprises a device for forming scented polymer pellets(e.g. polyethylene, polypropylene or mixtures of polyepsiloncaprolactone and polyethylene or polypropylene or co-polymers ofpolyvinyl acetate and polyethylene) which comprises a vat or container210 into which a mixture of polymer such a polyethylene and the cisand/or trans compound defined according to the structure: ##STR18## or amixture of perfume materials including as a key ingredient one or bothof the isomers defined according to the structure: ##STR19## is placed.

The container is closed by an air tight lid 228 clamped to the containerby clamps 265. A stirrer 273 traverses the lid or cover 228 in air tightmanner and is rotated in a suitable manner. A surrounding cylinder 212having heating coils which are supplied with electrical current throughcable 214 from a rheostat or control 216 is operated to maintain thetemperature inside the container 210 such that the polymer such aspolyethylene in the container will be maintained in the molten or liquidstate. It has been found advantageous to employ colorless, odorlesspolymer such as low-density polyethylene with a viscosity rangingbetween 180 and 220 centistokes and having a melting point in theneighborhood of 220° F. The heater 212 is operated to maintain the upperportion of the container 210 within the temperature range of from250°-350° F. An additional bottom heater 218 is regulated through acontrol 220 connected thereto through a connecting wire 222 to maintainthe lower portion of the container 210 within a temperature range offrom 250°-350° F.

In accordance with this aspect of the invention, a polymer such aspolyethylene or polypropylene is added to the container 210 and is thenheated from 10 to 12 hours whereafter a scent or aroma impartingmaterial containing the compound having the structure: ##STR20## isquickly added to the melt. The material must be compatible with thepolymer and forms a homogeneous liquid melt therewith. The heatresisting mixture, generally about 10-40% by weight of material havingthe structure: ##STR21## or mixture containing such compound or isomeris added to the polymer.

After the compound having the structure: ##STR22## or mixture containingsame is added to container 210, the mixture is stirred for a fewminutes, for example 5-15 minutes, and maintained within the temperatureranges indicated previously by the heating coils 212 and 218respectively. The controls 216 and 220 are connected through cables 224and 226 to a suitable supply of electric current for supplying the powerfor heating purposes.

Thereafter the valve "V" is opened permitting the mass to flow outwardlythrough a conduit 232 having a multiplicity of orifices 234 adjacent thelower side thereof. The outer end of the conduit 232 is closed so thatthe liquid polymer and substance containing compound having thestructure: ##STR23## will continuously drop through the orifice 234downwardly from the conduit 232. During this time the temperature of thepolymer and the compound having the structure: ##STR24## or mixturecontaining same in the container 210 is accurately controlled so that atemperature in the range of from 210° F. up to 275° F. will exist in thesubstance exiting in the conduit 232. The regulation of the temperaturethrough the control 216 and the control 220 is essential in order toinsure temperature balance to provide for the continuous dropping ordripping of molten polymeric material having the structure: ##STR25## ormixture containing same through the orifices 234 at a range which willinsure the formation of droplets 236 which will fall downwardly onto amoving conveyor belt 238 trained to run between conveyor wheels 240 and242 beneath the conduit 232. When the droplets 236 fall onto theconveyor belt 238, they form pellets 244 which harden almostinstantaneously and fall off the end of the conveyor 238 into acontainer 246 which is advantageously filled with water or some othersuitable liquid to insure the rapid cooling of each of the pellets. Thepellets 244 are then collected from the container 246 and packaged forshipment.

A feature of the invention is the provision for moistening the conveyorbelt 238 to insure the rapid formation of the solid polymer scentedpellets 244 without sticking to the belt. The belt 238 is advantageouslyof a material which will not normally stick to a melted polymer but themoistening means 248 insures a sufficiently cold temperature of the beltsurface for the adequate formation of the pellets 244. The moisteningmeans comprises a container 250 which is continuously fed with water 252to maintain a level 254 for moistening the sponge element 256 whichbears against the exterior surface of the belt 238.

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, medicinal products and flavoring compositions having pear,blackberry, peach or apricot flavors with sweet and musky aromacharacteristics and sweet and musky flavor characteristics and novelperfume compositions and perfumed articles having sweet, musky,animal-like aromas may be provided by the macrocyclic lactones havingthe structure: ##STR26##

It is to be understood that the structure: ##STR27## represents a "cis"as well as a "trans" isomer.

The macrocyclic lactones of our invention may be prepared by firstreacting the unsaturated alcohol having the structure: ##STR28## withthe ester having the structure: ##STR29## in the presence of an alkalimetal alkoxide and a solvent according to the reaction: ##STR30##

The catalyst used in the reaction may be an alkali metal alkoxide suchas sodium methoxide, sodium ethoxide, sodium isopropoxide, sodiumt-butoxide, potassium methoxide, potassium ethoxide, potassiumisopropoxide and potassium t-butoxide. The solvent used is one which isinert to the reactants as well as inert to the reaction products and, inaddition, is one which will not evaporate during the reaction at thedesired temperature. The desired temperature of reaction is betweenabout 90° and 140° C. The desired pressure is between about 0.5atmospheres up to about 10 atmospheres. Accordingly, an appropriatesolvent would be toluene, xylene or the like.

The most preferred solvent is toluene. The mole ratio of ester havingthe structure: ##STR31## to unsaturated alcohol having the structure:##STR32## may vary from about 0.5:1 up to about 1:0.5 with a preferredmole ratio of about 1:1. The concentration of alkali metal alkoxide inthe reaction mass may vary from about 5 grams per liter up to about 30grams per liter. The concentration of reactants in the reaction mass mayvary from about 2 moles per liter up to about 6 moles per liter.

At the end of the first reaction, the solvent is stripped and thereaction mass is distilled to create a product boiling at about 2.5mm/Hg pressure at 132°-135° C.

This reaction product is then reacted according to an internalmetathesis reaction according to the following reaction: ##STR33## Theconditions of this metathesis reaction are set forth in the article byTsuji and Hashiguchi, Journal of Organometallic Chemistry, 218(1981),69-80, the disclosure of which is incorporated by reference herein. Thereaction is carried out in the presence of catalysts such as WCl₆ andWOCl₄ as primary catalysts and tetramethyl tin, tetramethyl lead, Cp₂TiCH₃ taken twice and Cp₂ ZrCH₃ taken twice as co-catalysts.

At the end of the reaction, the resulting product having the structure:##STR34## is isolated by means of extraction and distillation. Theresulting product may then be separated into its cis and trans isomersby standard preparative chromatographic techniques.

When the macrocyclic lactones of our invention are used as food flavoradjuvants, the nature of the co-ingredients included with saidmacrocyclic lactones in formulating the product composition will serveto alter the organoleptic characteristics of the ultimate foodstufftreated therewith.

As used herein in regard to flavors, the terms "alter" and "modify" intheir various forms means "supplying or imparting flavor character ornote to otherwise bland, relatively tasteless substances or augmentingthe existing flavor characteristic where a natural flavor or syntheticflavor or mixture of natural and synthetic flavors is deficient in someregard, or supplementing the existing flavor impression to modify itsquality, character or taste".

As used herein, the term "enhance" is intended to mean theintensification (without effecting a change in kind of quality or aromaor taste) of one or more taste and/or aroma nuances present in theorganoleptic impression of a consumable material, e.g., foodstuff,tobacco, chewing gum, medicinal product, perfume composition or perfumedarticle.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "chewing gum" is intended to mean a compositionwhich comprises a substantially water-insoluble, chewable plastic gumbase such as chicle, or substitutes therefor, including jelutung,guttakay rubber and/or certain comestible natural or synthetic resins orwaxes. Incorporated within the gum base, in admixture therewith may beplasticizers or softening agents, e.g., glycerine; and a flavoringcomposition which incorporates the macrocyclic lactones of ourinvention, and, in addition, sweetening agents which may be sugars,including sucrose or dextrose and/or artificial sweeteners includingdipeptides, cyclamates and saccharin. Other optional ingredients mayalso be present.

The term "medicinal product" includes both solids and liquids which areingestible, non-toxic materials having medicinal value such as coughsyrups, cough drops, toothpaste, aspirin and chewable medicinal tabletsas further exemplified herein.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use being extensivelydescribed in the relevant literature. Such material is required to be"ingestibly" acceptable and thus non-toxic or otherwise non-deleterious.Particularly critical is the additional requirement that such materialbe organoleptically compatible with the macrocyclic lactones encompassedwithin the scope of our invention. Also critical is the additionalrequirement that such material be nonreactive (within the range ofstorage conditions and room temperature use conditions) with themacrocyclic lactones.

Accordingly, such materials which may in general be characterized asflavoring adjuvants or vehicles comprise broadly stabilizers,thickeners, surface active agents, conditioners, other flavorants andflavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene,(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers, and the like, e.g., agaragar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids,carbohydrates, starches, pectins, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim silk powder, hexoses, pentoses,disaccharides, e.g., sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents, such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, turmeric and curcuma and thelike, firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aliminumcalcium sulfate and tribasic calcium phosphate; enzymes, yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid, cis andtrans 2-methyl-2-pentenoic acid, and cis and trans 2-methyl-3-pentenoicacid; ketones and aldehydes, e.g., acetaldehyde, acetophenone, acetone,acetyl methyl carbinol, acrolein, n-butanal, crotonal, diacetyl, beta,beta-dimethyl-acrolein, n-hexanal, 2-hexenal, cis-3-hexenal, 2-heptenal,4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, 2-pentanone, 2-pentenal and propanal; alcohols suchas 1-butanol, benzyl alcohol, 1-borneol, trans-3-buten-1-ol, ethanol,geraniol, 1-hexanol, 2-heptenol-1, trans-3-hexenol-1, cis-3-hexen-1-ol,3-methyl-3-buten-1-ol, 1-penten-2-ol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate; esters, suchas butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate,ethyl butyrate, ethyl caproate, ethyl cinnamate, ethyl crotonate, ethylformate, ethyl isobutyrate, ethyl isovalerate, ethylalpha-methylbutyrate, ethyl propionate, ethyl salicylate,trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, n-hexylbutyrate, isoamyl acetate, isopropyl butyrate, methyl acetate,methyl-n-butyrate, methyl caproate, methyl isobutyrate,alpha-methyl-n-butyrate, n-propyl acetate, n-amyl acetate,n-amyl-n-butyrate, benzyl salicylate, dimethyl anthranilate, ethylmethylphenylglycidate, ethyl succinate, isobutyl cinnamate, and terpenylacetate; lactones, such as delta-decalactone, delta-undecalactone,delta-nonyl-lactone, gamma-undecalactone, gamma-dodecalactone and gammanonyl-lactone as well as "peach" lactones; essential oils, such asjasmine absolute, rose absolute, orris absolute, lemon essential oil,Bulgarian rose, yara yara, natural raspberry oil and vanilla; sulfides,e.g., methyl sulfide and other materials such as maltol, acetoin andacetals (e.g., 1,1-diethoxyethane, 1,1-dimethoxyethane anddimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff whether simulated or natural, and should, in any event,be capable of providing an environment in which the macrocyclic lactonescan be dispersed or admixed to provide a homogeneous medium. Inaddition, selection of one or more flavoring adjuvants, as well as thequantities thereof will depend upon the precise organoleptic characterdesired in the finished product. Thus, in the case of flavoringcompositions, ingredient selection will vary in accordance with thefoodstuff to which the flavor and aroma are to be imparted. Incontradistinction, in the preparation of solid products, e.g. simulatedfoodstuffs, ingredients capable of providing normally solid compositionsshould be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of themacrocyclic lactones employed in a particular substance can vary over arelatively wide range whereby specific desired organoleptic effects(having particular reference to the nature of the product) are achieved.Thus, correspondingly greater amounts would be necessary in thoseinstances wherein the ultimate food composition to be flavored isrelatively bland to the taste, whereas relatively minor quantities maysuffice for purposes of enhancing the composition merely deficient innatural flavor or aroma. The primary requirement is that the amountselected be effective, i.e. sufficient to alter, modify or enhance theorganoleptic characteristics of the parent composition, whetherfoodstuff per se or flavoring composition.

The use of insufficient quantities of the macrocyclic lactones will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities prove needlessly costly and in extremecases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, it has been foundthat quantities of the macrocyclic lactones ranging from a small buteffective amount, e.g. 0.0001 parts per million up to about 50 parts permillion by weight based on total composition are suitable.Concentrations in excess of the maximum quantity stated are not normallyrecommended since they fail to provide commensurate enhancement oraugmentation of organoleptic properties. In those instances wherein themacrocyclic lactones are added to the foodstuff as an integral componentof a flavoring composition, it is, of course, essential that the totalquantity of flavoring composition employed be sufficient to yield aneffective concentration (of macrocyclic lactones) in the foodstuffproduct.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the macrocyclic lactones in concentrationsranging from about 0.01% up to about 15% by weight based on the totalweight of the said flavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the macrocyclic lactones with, forexample, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spraydrying the resultant mixture whereby to obtain theparticulate solid product. Pre-prepared flavor mixes in powder form,e.g. a fruit-flavored powder mix are obtained by mixing the dried solidcomponents, e.g. starch, sugar and the like, and the macrocycliclactones in a dry blender until the requisite degree of uniformity isachieved.

It is presently preferred to combine with the macrocyclic lactones, thefollowing adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Vanillin;

Methyl cinnamate;

Ethyl pelargonate;

Methyl anthranilate;

Isoamyl acetate;

Isobutyl acetate;

Alpha ionone;

β-Damascone;

β-Damascenone;

Ethyl butyrate;

Acetic acid;

n-Hexyl acetate;

n-Hexyl isobutyrate;

Trans-2-hexenal;

Linalyl isobutyrate;

n-Hexyl-2-methyl-n-butyrate;

Gamma-undecalactone;

Gamma-nonalactone;

Gamma decalactone;

Delta undecalactone;

Delta dodecalactone;

Delta nonyl lactone;

"Peach" lactone;

Naphthyl ethyl ether;

Diacetyl;

Apple Fusel Oil;

Sauge Sclaree;

Coriander Oil;

Ethyl acetate;

Anethole;

Isoamyl-n-butyrate;

Ethyl-2-methyl-cis-3-pentenoate;

Cis-3-hexenol-1;

2-Methyl-cis-3-pentenoic acid;

2-Methyl-2-pentenoic acid;

Elemecine(4-allyl-1,2,6-trimethoxy benzene);

Isoelemecine(4-propenyl-1,2,6-trimethoxy benzene); and

2-(4-hydroxy-4-methylpentyl)norbornadiene prepared according to U.S.Pat. No. 3,886,289.

The macrocyclic lactones and one or more auxiliary perfume ingredients,including, for example, alcohols, aldehydes, nitriles, esters, cyclicesters, ketones and natural essential oils, may be admixed so that thecombined odors of the individual components produce a pleasant anddesired fragrance particularly and preferably in musk and "animal-like"fragrances. Such perfume compositions usually contain (a) the main noteor the "bouquet" or foundation stone of the composition; (b) modifierswhich round off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to its particular olfactory characteristics, but the over-alleffect of the perfume composition will be the sum of the effects of eachof the ingredients. Thus, the macrocyclic lactones can be used to alterthe aroma characteristics of a perfume composition, for example, byutilizing or moderating the olfactory reaction contributed by at leastone other ingredient in the composition.

The amount of the macrocyclic lactones of our invention which will beeffective in perfume compositions depends on many factors, including theother ingredients, their amounts and the effects which are desired. Ithas been found that perfume compositions containing as little as 0.01%of the macrocyclic lactones and even less (e.g. 0.005%) can be used toimpart rich, animal-musk and sweet notes to soaps, anionic, cationic,nonionic and zwitterionic detergents, fabric softener articles, perfumedpolymers, cosmetics and other products. The amount employed can range upto 10% of the fragrance components and will depend on considerations ofcost, nature of the end product, the effect desired on the finishedproduct and the particular fragrance sought.

The macrocyclic lactones are useful, taken alone or in perfumecompositions as olfactory components in anionic, cationic and nonionicdetergents, soaps, fabric softener compositions and fabric softenerarticles for use in clothes driers (e.g. "BOUNCE"®, a registeredtrademark of the Procter & Gamble Company of Cincinnati, Ohio), spaceodorants and deodorants, perfumes, colognes, toilet water, bathpreparations, such as bath oils, and bath solids; hair preparations suchas lacquers, brilliantines, creams, deodorants, hand lotions and sunscreens, powders such as talcs, dusting powders, face powders and thelike. When used as an olfactory component in perfume compositions orperfumed articles, such as anionic, cationic and nonionic detergents andin fabric softener compositions and fabric softener articles (e.g. foruse in clothing driers) as little as 0.05% of the macrocyclic lactonesof our invention will suffice to impart rich, animal-musk and sweetnotes. Generally no more than 5% of the macrocyclic lactones based onthe ultimate end product is required in the perfume composition or inthe perfumed article.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle or carrier for the macrocyclic lactones.The vehicle can be a liquid such as a non-toxic alcohol, a non-toxicglycol, or the like. The carrier can also be an absorbent solid such asa gum (e.g. gum arabic) or components for encapsulating the composition(such as gelatin) as by means of coacervation.

Macrocyclic lactones of our invention may be blended into polymers whenforming a perfumed polymer by means of extrusion using a single ordouble screw extruder or technique such as that set forth in U.S. Pat.No. 4,247,498 issued on Jan. 27, 1981, the disclosure of which isincorporated by reference herein, which discloses microporous polymerswhich are capable of containing volatile substances such as perfumes andthe like and forms ranging from films to blocks and intricate shapesfrom synthetic thermoplastic polymers such as olefinic condensation oroxidation polymers. Other techniques of blending the macrocycliclactones of our invention with polymers are exemplified in U.S. Pat. No.3,505,432 (the specification for which is incorporated by referenceherein) which discloses a method for scenting a polyolefin with suchmaterials as the macrocyclic lactones of our invention which comprises:

(a) mixing a first amount of the liquid polyolefin (e.g. polyethylene orpolypropylene) with a relatively large amount of scent-impartingmaterial (in this case the macrocyclic lactones of our invention) toform a flowable mass;

(b) forming drops of said mass and causing substantially instantaneoussolidification of said drops into polyolefin pellets having a relativelylarge amount of such scent-imparting materials as the macrocycliclactones of our invention imprisoned therein;

(c) melting said pellets with a second amount of polyolefin and saidsecond amount being larger than the first amount; and

(d) solidifying the melt of (c).

The following Examples I and II set forth techniques for preparing themacrocyclic lactones of our invention. The examples following ExampleII, Examples III, et seq. indicate organoleptic uses of the macrocycliclactones of our invention.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF DEHYDROEXALTOLIDE INTERMEDIATE ##STR35##

Into a one liter flask equipped with stirrer, thermometer, Vigreuxcolumn and reflux head and nitrogen blanket apparatus are placed 200grams (2 moles) of 5-hexenol-1, 396 grams (2 moles) ofmethyl-10-undecylenate, 12.5 grams of sodium methoxide and 250 mltoluene.

The resulting mixture is heated to reflux and the methanol reactionproduct is distilled off via a short column with reflux head. Thedistillation of the methanol continues until the vapor temperatureremains at 105°-110° C. and the liquid temperature remains at 145°-150°C.

The reaction mass is acidified with aqueous acetic acid and washed withwater. The toluene is stripped off and the resulting product is thendistilled through a 14" Vigreux column with reflux head yielding 460grams of product (desired boiling point 132°-135° C. at 2.5 mm/Hg). Thedistillation product contains the following fractions:

    ______________________________________                                                Vapor   Liquid             Weight of                                  Fraction                                                                              Temp.   Temp.       Vacuum Fraction                                   Number  (°C.)                                                                          (°C.)                                                                              mm/Hg  (grams)                                    ______________________________________                                        1       66/65   144/152     2.5/2.5                                                                               3.7                                       2       125     144         2.4    13.0                                       3       126     148                22.1                                       4       131     149         3.0    31.4                                       5       130     149         2.4    34.9                                       6       132     140         3.0    35.9                                       7       134     150         2.4    41.8                                       8       136     151         2.6    34.3                                       9       137     152         2.7    41.6                                       10      146     156         2.9    44.7                                       11      147     157         4.2    29.9                                       12      148     158         6.0    22.8                                       13      131     152         2.5    40.6                                       14      132     158         2.5    38.5                                       15      135     168         2.5    27.2                                       16      151     190         2.5    15.5                                       17       75     220         2.5     5.3                                       ______________________________________                                    

FIG. 1 is the NMR spectrum for the compound having the structure:##STR36## (conditions: Field Strength: 100 MHz; Solvent: CFCl₃).

FIG. 2 is the infra-red spectrum for the compound having the structure:##STR37##

Fractions 6-15 are bulked and used in Example II.

EXAMPLE II PREPARATION OF DEHYDROEXALTOLIDE ##STR38##

100 ml anhydrous chlorobenzene and 478.2 mg of tungsten hexachloride aremixed under nitrogen blanket for 30 minutes. 6.6 grams of5-hexenyl-10-undecylenate prepared according to Example I are added tothe reaction mass under a nitrogen blanket. The reaction mass is stirredat 40° C. for 30 minutes. 525 microliters of tetramethyl tin are thenadded to the reaction mass with stirring. The reaction mass is stirredfor 60 minutes at 40° C. The resulting mixture is added over a 3 hourperiod to 300 ml of monochlorobenzene. The resulting mixture is heatedto 80°-90° C. for 3-4 hours and then aged for 7 hours. To the reactionmixture 400 microliters of tetramethyl tin is added and over a period of2-3 hours, a solution of 371 mg of tungsten hexachloride dissolved in100 ml chlorobenzene is added to the reaction mass at 85°-90° C. Thereaction mass is aged for 7 hours (conversion: 45%).

An additional 350 microliters of tetramethyl tin is added to thereaction mass and dropwise over a 2-3 hour period, 307 mg of tungstenhexachloride in 100 ml chlorobenzene is added to the reaction mass at85°-90° C. The reaction mass is aged for 7 hours (conversion: 95%).

The reaction mass is stirred with water for 30 minutes and washed with 4volumes of water.

The chlorobenzene is stripped off leaving 5.44 grams of oil. Thereaction product is then distilled at 1.8 mm/Hg at 130°-135° C. Theresulting product is then chromatographed and by means of preparativecolumn chromatography, the cis isomer is separated from the transisomer.

FIG. 3 is the GLC profile for the reaction product prior to distillationof Example II. The peak indicated by reference numeral "31" is the peakfor the starting material having the structure: ##STR39##

The peak indicated by reference numeral "32" is the peak for the transisomer of the compound having the structure: ##STR40##

The peak indicated by reference numeral "33" is the peak for the cisisomer having the structure: ##STR41## (GLC conditions: 10'×0.25" 10%Carbowax column programmed at 150°-225° C. at 8° C. per minute).

FIG. 4 is the NMR spectrum for the trans isomer of the compound havingthe structure: ##STR42## (conditions: Field Strength: 100 MHz; Solvent:CFCl₃).

FIG. 5 is the infra-red spectrum for the trans isomer of the compoundhaving the structure: ##STR43##

FIG. 6 is the NMR spectrum for the cis isomer of the compound having thestructure: ##STR44## (conditions: Field Strength: 100 MHz; Solvent:CFCl₃).

FIG. 7 is the infra red spectrum for the cis isomer of the compoundhaving the structure: ##STR45##

EXAMPLE III MUSK PERFUME FORMULATION

The following musk perfume formulation is prepared:

    ______________________________________                                        Ingredients        Parts by Weight                                            ______________________________________                                        Musk ambrette      200                                                        Musk ketone        200                                                        Beta ionone         50                                                        Vetiveryl acetate   50                                                        Sandalwood oil     100                                                        Benzyl benzoate    400                                                        Mixture of cis and trans                                                                          20                                                        isomers having the structure:                                                  ##STR46##                                                                    prepared according to                                                         Example 2                                                                     ______________________________________                                    

in Example 23.

The mixture of compounds having the structure: ##STR47## imparts to thismusk formulation a natural "animal musk", sweet, tonka-like andcoumarin-like aroma causing it to be more natural-like. Accordingly,this formulation can be described as "musky, with animal-like, sweet andcoumarin-line undertones".

EXAMPLE IV PREPARATION OF COSMETIC POWDER COMPOSITIONS

Cosmetic powder compositions are preapred by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table I below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table I below:

                  TABLE I                                                         ______________________________________                                        Substance         Aroma Description                                           ______________________________________                                        Mixture of "cis" and                                                                            A sweet, jusky, animalic,                                   "trans" isomers having                                                                          tonka-like and coumarin-                                    the structure:    like aroma.                                                  ##STR48##                                                                    Perfume composition of                                                                          Musky with animal-like,                                     Example III.      sweet and coumarin-like                                                       undertones.                                                 "Cis" isomer of the                                                                             A sweet, musky, animal-like,                                compound having the                                                                             tonka-like and coumarin-like                                structure:        aroma.                                                       ##STR49##                                                                    "Trans" isomers of the                                                                          A sweet, musky, animalic                                    compound having the                                                                             tonka-like and coumarin-like                                structure:        aroma.                                                       ##STR50##                                                                    ______________________________________                                    

EXAMPLE V PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976 incorporated by reference herein) with aroma nuances as setforth in Table I of Example IV, are prepared containing 0.10%, 0.15%,0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in Table I ofExample IV. They are prepared by adding and homogeneously mixing theappropriate quantity of substance set forth in Table I of Example IV inthe liquid detergent. The detergents all possess excellent aromas as setforth in Table I of Example IV, the intensity increasing with greaterconcentrations of substance as set forth in Table I of Example IV.

EXAMPLE VI PREPARATION OF COLOGNES AND HANDKERCHIEF PERFUMES

Compositions as set forth in Table I of Example IV are incorporated intocolognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions; andinto handkerchief perfumes at concentrations of 15%, 20%, 25% and 30%(in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table I of ExampleIV are imparted to the colognes and to the handkerchief perfumes at alllevels indicated.

EXAMPLE VII PREPARATION OF SOAP COMPOSITIONS

One hundred grams of soap chips (per sample) (IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table I of Example IV untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of three hours and the resulting liquids are placed intosoap molds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table I of Example IV.

EXAMPLE VIII PREPARATION OF SOLID DETERGENT COMPOSITIONS

Detergents are prepared using the following ingredients according toExample I of Canadian Pat. No. 1,007,948 (incorporated by referenceherein):

    ______________________________________                                        Ingredient          Percent by Weight                                         ______________________________________                                        "Neodol ® 45-11"                                                                              12                                                        (a C.sub.14 -C.sub.15 alcohol ethoxylated                                     with 11 moles of                                                              ethylene oxide)                                                               Sodium carbonate    55                                                        Sodium citrate      20                                                        Sodium sulfate, water brighteners                                                                 q.s.                                                      ______________________________________                                    

This detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table I of Example IV. Each ofthe detergent samples has an excellent aroma as indicated in Table I ofExample IV.

EXAMPLE IX

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated herein by reference),nonwoven cloth substrates useful as drier-added fabric softeningarticles of manufacture are prepared wherein the substrate, thesubstrate coating, the outer coating and the perfuming material are asfollows:

1. a water "dissolvable" paper ("Dissolvo paper")

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the substances as set forth in Table I of Example IV.

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table I of Example IV, supra, consist of a substrate coating having aweight of about 3 grams per 100 square inches of substrate; a firstcoating located directly on the substrate coating consisting of about1.85 grams per 100 square inches of substrate; and an outer coatingcoated on the first coating consisting of about 1.4 grams per 100 squareinches of substrate. One of the substances of Table I of Example IV isadmixed in each case with the outer coating mixture, thereby providing atotal aromatized outer coating weight ratio to substrate of about 0.5:1by weight of the substrate. The aroma characteristics are imparted in apleasant manner to the head space in a drier on operation thereof ineach case using said drier-added fabric softener nonwoven fabrics andthese aroma characteristics are described in Table I of Example IV,supra.

EXAMPLE X HAIR SPRAY FORMULATIONS

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 co-polymer manufactured by the GAF Corporation of 140 West51st Street, New York, N.Y. in 91.62 grams of 95% food grade ethanol.8.0 grams of the polymer is dissolved in the alcohol. The followingingredients are added to the PVP/VA alcoholic solution:

    ______________________________________                                        Dioctyl sebacate    0.05   weight percent                                     Benzyl alcohol      0.10   weight percent                                     Dow Corning 473 fluid                                                                             0.10   weight percent                                     (prepared by the Dow Corning                                                  Corporation)                                                                  Tween 20 surfactant 0.03   weight percent                                     (prepared by ICI America                                                      Corporation)                                                                  One of the perfumery                                                                              0.10   weight percent                                     substances as set forth                                                       in Table I of Example IV,                                                     supra                                                                         ______________________________________                                    

The perfuming substances as set forth in Table I of Example IV add aromacharacteristics as set forth in Table I of Example IV which are ratherintense and aesthetically pleasing to the users of the soft-feel,good-hold pump hair sprays.

EXAMPLE XI CONDITIONING SHAMPOOS

Monamid CMA (prepared by the Mona Industries Company) (3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation) (1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.). This material is "Composition A".

Gafquat® 755N polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weightpercent sodium sulfite and 1.4 weight percent polyethylene glycol 6000distearate produced by Armak Corporation. This material is "CompositionB".

The resulting Composition A and Composition B are then mixed in a 50:50weight ratio of A:B and cooled to 45° C. and 0.3 weight percent ofperfuming substance as set forth in Table I of Example IV is added tothe mixture. The resulting mixture is cooled to 40° C. and blending iscarried out for an additional one hour in each case. At the end of thisblending period, the resulting material has a pleasant fragrance asindicated in Table I of Example IV.

EXAMPLE XII

Scented polyethylene pellets having a pronounced scent as set forth inTable I of Example IV are prepared as follows:

75 pounds of polyethylene of a melting point of about 220° F. are heatedto about 230° F. in a container of the kind illustrated in FIGS. 8 and9. 25 Pounds of each of the perfume materials of Table I of Example IVsupra, are then added quickly to the liquified polyethylene. The lid 228is put in place and the agitating means 273 are actuated. Thetemperature is maintained at about 225° F. and the mixing is thencontinued for about 5-15 minutes. The valve 230 is then opened to allowflow of the molten polyethylene enriched with each of the aromasubstance-containing materials to exit through the orifices 234. Theliquid falling through the orifices 234 solidify almost instantaneouslyupon impact with the moving, cooled conveyor 238. Solid polyethylenebeads or pellets 244 having pronounced aromas as set forth in Table I ofExample IV supra are then formed. Analysis demonstrates that the pelletscontain about 25% of each of the perfume substances of Table I ofExample IV so that almost no losses of the scenting substance occur.These pellets may be called master pellets.

50 pounds of the scent-containing master pellets are then added to 1,000pounds of unscented polyethylene powder and the mass is heated to theliquid state. The liquid is molded into thin sheets or films. The sheetsor films have a pronounced aroma as set forth in Table I of Example IVsupra. The sheets are also fabricated into garbage bags which havearomas as set forth in Table I of Example IV supra.

EXAMPLE XIII

The following basic mangoflavor formulation is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Vanillin              2.0                                                     Hexyl Acetate         8.0                                                     Hexyl Isobutyrate     20.0                                                    Trans-2-hexenal (10% in propylene                                                                   2.0                                                     glycol)                                                                       β-Caryophyllene  8.2                                                     1-Methyl-3-n-propyl-2,4-oxathiane                                                                   32.0                                                    1-Ethyl-3-n-propyl-4,2-oxathiane                                                                    2.5                                                     1-Methyl-3-isopropyl-2,4-oxathiane                                                                  3.8                                                     Mango skin extract ex Venezuela                                                                     14.5                                                    n-Hexanal             0.5                                                     Apple Fusel Oil       10.0                                                    Linalyl Isobutyrate   0.5                                                     Hexyl-2-methylbutyrate                                                                              10.0                                                    Sauge Sclaree (10% in propylene glycol)                                                             0.5                                                     Coriander Oil         0.5                                                     Food grade ethyl alcohol (aqueous, 95%)                                                             146.0                                                   Propylene glycol      800.0                                                   ______________________________________                                    

To a portion of the above basic mango formulation 0.02% by weight of acis:trans mixture of the compound having the structure: ##STR51## isadded. To another portion of the basic mango formulation nothing isadded. Both flavor formulations are compared at the rate of 50 ppm inwater and evaluated by a blind bench panel of four experienced tasters.All of the tasters of the bench panel state that the flavor containingthe mixture of "cis" and "trans" isomers of the compound having thestructure: ##STR52## has a more natural, riper mango character. Thismango character is enhanced and longer lasting as a result of theaddition of the mixture of "cis" and "trans" isomers of the compoundhaving the structure: ##STR53## Therefore, the flavor formulationcontaining the mixture of "cis" and "trans" isomers of the compoundhaving the structure: ##STR54## is unanimously preferred.

EXAMPLE XIV A. POWDER FLAVOR

Twenty grams of the flavor composition of Example XIII which flavorcomposition contains a mixture of cis and trans isomers of the compoundhaving the structure: ##STR55## prepared according to Example II isemulsified in a solution containing 300 grams gum acacia and 700 gramswater. The emulsion is spray-dried with a Bowen Lab Model Drierutilizing 250 c.f.m. of air with an inlet temperature of 500° F. andoutlet temperature of 200° F. and a wheel speed of 50,000 r.p.m.

B. PASTE BLEND

The following mixture is then prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Liquid flavor composition                                                                           48.4                                                    of Example XIII                                                               Cab-O-Sil M-5         3.2                                                     (Brand of Silica produced by                                                  the Cabot Corporation of                                                      125 High Street, Boston,                                                      Mass. 02110);                                                                 Physical properties:                                                          Surface area: 200 m.sup.2 /gm                                                 Nominal particle Size: 0.012 microns                                          Density: 2/3 lbs./cu. ft.                                                     ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid flavor composition withvigorous stirring, thereby resulting in a viscous liquid. 48.4 parts byweight of the powder flavor composition prepared in Part A is thenblended into the said viscous liquid with stirring at 25° C. for aperiod of 30 minutes, resulting in a thixotropic sustained releasedflavor paste.

EXAMPLE XV CHEWING GUM

100 parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XIVB. 300 parts of sucroseand 100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resulting chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant long-lastingmango flavor.

EXAMPLE XVI TOOTHPASTE FORMULATION

The following separate groups of ingredients are prepared:

    ______________________________________                                        Group "A"                                                                     30.200        Glycerin                                                        15.325        Distilled Water                                                 .100          Sodium Benzoate                                                 .125          Saccharin Sodium                                                .400          Stannous Fluoride                                               Group "B"                                                                     12.500        Calcium Carbonate                                               37.200        Dicalcium Phosphate                                                           (Dihydrate)                                                     Group "C"                                                                     2.000         Sodium n-Lauroyl Sarcosinate                                                  (foaming agent)                                                 Group "D"                                                                     1.200         Flavor Material of Example XIVB                                 100.00 (Total)                                                                ______________________________________                                    

PROCEDURE:

1. To ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodiumn-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste when used in a normal toothbrushing procedureyields a pleasant mango flavor of constant strong intensity throughoutsaid procedure (1-1.5 minutes).

EXAMPLE XVII CHEWABLE VITAMIN TABLETS

The flavor material produced according to the process of Example XIVB isadded to a chewable vitamin tablet formulation at a rate of 5 gm/kgwhich chewable vitamin tablet formulation is prepared as follows:

    ______________________________________                                        Ingredients          Gms/1000 Tablets                                         ______________________________________                                        Vitamin C (ascorbic acid)                                                                          70.0                                                     as ascorbic acid-solution mixture 1:1                                         Vitamin B.sub.1 (thiamine mononitrate)                                                             4.0                                                      as Rocoat ® thiamine mononitrate 33%                                      (Hoffman La Roche)                                                            Vitamin B.sub.2 (riboflavin)                                                                       5.0                                                      as Rocoat ® riboflavin 331/3%                                             Vitamin B.sub.6 (pyridoxine hydrochloride)                                                         4.0                                                      as Rocoat ® pyridoxide hydrochloride                                      331/3%                                                                        Niacinamide          33.0                                                     as Rocoat ® niacinamide 331/3%                                            Calcium pantothenate 11.5                                                     Vitamin B.sub.12 (cyanocobalamin)                                                                  3.5                                                      as Merck 0.1% in gelatin                                                      Vitamin E (dl-alpha tocopheryl acetate                                                             6.6                                                      as dry Vitamin E acetate 331/3% Roche                                         d-Biotin             0.044                                                    Certified lake color 5.0                                                      Flavor of Example XIVB                                                                             2.5                                                      Sweetener-sodium saccharin                                                                         1.0                                                      Magnesium stearate lubricant                                                                       10.0                                                     Mannitol q.s. to make                                                                              500.0                                                    ______________________________________                                    

Preliminary tablets are prepared by slugging, with flatfaced punches andgrinding the slugs to 14 mesh. 13.5 grams dry Vitamin A acetate and 0.6grams Vitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 grams each.

Chewing of the resultant tablet yields a pleasant, long-lasting,consistently strong mango flavor for a period of 12 minutes.

What is claimed is:
 1. A process for augmenting or enhancing the aroma of a perfumed article comprising the step of intimately admixing with said perfumed article, an aroma augmenting or enhancing quantity of the "cis" or "trans" isomer or mixture of "cis" and "trans" isomers of the compound defined according to the structure: ##STR56##
 2. The process of claim 1 wherein the perfumed article is a solid or liquid anionic, cationic, nonionic or zwitterionic detergent.
 3. The process of claim 1 wherein the perfumed article is a fabric softener composition or fabric softener article. 